首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2171篇
  免费   357篇
  国内免费   243篇
化学   1566篇
晶体学   20篇
力学   105篇
综合类   10篇
数学   292篇
物理学   778篇
  2024年   6篇
  2023年   59篇
  2022年   63篇
  2021年   65篇
  2020年   86篇
  2019年   78篇
  2018年   73篇
  2017年   64篇
  2016年   94篇
  2015年   75篇
  2014年   99篇
  2013年   135篇
  2012年   163篇
  2011年   183篇
  2010年   103篇
  2009年   129篇
  2008年   130篇
  2007年   128篇
  2006年   128篇
  2005年   104篇
  2004年   83篇
  2003年   60篇
  2002年   60篇
  2001年   65篇
  2000年   56篇
  1999年   64篇
  1998年   38篇
  1997年   45篇
  1996年   46篇
  1995年   37篇
  1994年   21篇
  1993年   28篇
  1992年   30篇
  1991年   29篇
  1990年   23篇
  1989年   10篇
  1988年   9篇
  1987年   10篇
  1986年   9篇
  1985年   8篇
  1984年   9篇
  1983年   6篇
  1982年   10篇
  1981年   5篇
  1980年   4篇
  1979年   5篇
  1978年   3篇
  1976年   4篇
  1974年   3篇
  1973年   5篇
排序方式: 共有2771条查询结果,搜索用时 15 毫秒
101.
The influence of the flashlamp pump current pulse shape on Er:YAG laser efficiency and laser rod thermal focusing was studied theoretically and experimentally. Two pulse shapes, PFN (Pulse Forming Network) and VSP (Variable Square Pulse), were considered. Theoretical modeling and experimental measurements show that the pump pulse shape itself does not have a significant influence on the Er:YAG laser efficiency or thermal focusing. Instead, the major parameter influencing Er:YAG laser efficiency and thermal focusing was found to be the overall pulse duration. For PFN pulses, rise and fall times directly define the overall pulse duration, and therefore do have influence on thermal focusing. By contrast, VSP pulse duration is defined by the externally controlled on-time of the switching transistor. For square shaped pulses, short rise and fall times do not have a direct beneficial influence on thermal lensing.  相似文献   
102.
邓桂胜  莫宏华  罗景  汤力 《有机化学》2012,32(11):2177-2180
在氧化银和碘化钾存在下,磺酰氯与肟室温反应合成一系列O-磺酰基肟.芳香醛肟和酮肟作为底物,产率56%~87%.不过,对硝基苯甲醛肟、脂肪醛肟及α,β-不饱和醛肟作为该反应底物时,没有获得目标产物.  相似文献   
103.
Fanyang Mo  Fei Li  Di Qiu  Yan Zhang  Jianbo Wang 《中国化学》2012,30(10):2297-2302
The study toward the total synthesis of (R)‐(+)‐harmicine is reported in this paper. The enantioselective synthesis of pyrrolidinone, the main backbone of of (R)‐(+)‐harmicine, has been completed by the methodology based on photo‐induced Wolff rearrangement of α‐diazo‐β‐carbonyl compounds.  相似文献   
104.
Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN4C8H8) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3pz leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3pz results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si.  相似文献   
105.
106.
设A是R~n上的一个m阶可导函数,且D~λA∈Λ_β(0β1,|λ|=m),Ω(x,z)∈L~∞(R~n)×L~s(S~(n-1))(sn/(n-β))是零阶齐次函数且关于变量z满足消失条件.该文证明了广义高阶Marcinkiewicz积分交换子μ_Ω~A及其变形μ_Ω~A在Herz型Hardy空间的有界性.  相似文献   
107.
The effect of WO3 on thermal behaviour and thermal stability of ZnO–P2O5–WO3 glasses prepared in compositional series (100 ? x)[0.5ZnO–0.5P2O5] ? xWO3 (x = 0–60) was investigated by heating microscopy and the results were correlated with the results determined by conventional thermodilatometry and differential thermal analysis. Thermoanalytical studies showed that the glass transformation temperature and dilatation softening temperature increase with increasing WO3 content while thermal expansion coefficient decreases. The highest stability towards crystallization possess glasses containing 20–30 mol% WO3. Major compounds formed by the crystallization of the glasses were Zn(PO3)2, WO3 and W18P2O59. The values of sphere temperature, hemisphere temperature and flow temperature obtained using heating microscopy were strongly influenced by the degree of crystallization process at the sintering.  相似文献   
108.
Pyrolysis is one important way to treat polystyrene waste and upcycle it into useful materials. A comparative pyrolysis study of virgin polystyrene (VPS) and two types of commonly used polystyrene products, expanded polystyrene (EPS) and polystyrene container (CPS) was carried out. Various values were found in the thermodynamic study and kinetic study of VPS, EPS, and CPS pyrolysis, suggesting distinct thermal degradation characteristics of these materials. The energy barrier order of the pyrolysis processes was EPS, CPS, VPS, showing activation energy of 230, 219, and 145 kJ mol?1, respectively. The order of amount of heat absorbed was EPS, CPS, VPS, with enthalpy of 224, 213, and 139 kJ mol?1, respectively. The reaction favorability order was EPS, CPS, and VPS with Gibbs free energy of 118, 132, and 210 kJ mol?1, respectively. Thermogravimetric analysis indicated the use of high heating rate would increase the reaction rate and shorten the reaction time. Product evolution profiles showed that VPS and CPS pyrolysis produced mainly aromatics, while EPS pyrolysis produced aromatics at the initial phase of the reaction and aliphatic hydrocarbon at the latter phase. The diverse pyrolysis behaviors of VPS, EPS, and CPS demonstrated that an examination on different polystyrene materials was desired to optimize the pyrolysis conditions and product distribution, and thus benefit the process of valuable materials recovery.  相似文献   
109.
Silanol groups on a silica surface affect the activity of immobilized catalysts because they can influence the hydrophilicity/hydrophobicity, matter transfer, or even transition state in a catalytic reaction. Previously, these silanol groups have usually been passivated by using surface‐passivation reagents, such as alkoxysilanes, bis‐silylamine reagents, chlorosilanes, etc., and surface passivation has typically been found in mesoporous‐silicas‐supported molecular catalysts and heteroatomic catalysts. However, this property has rarely been reported in mesoporous‐silicas‐supported metal‐nanoparticle catalysts. Herein, we prepared an almost‐superhydrophobic SBA‐15‐supported gold‐nanoparticle catalyst by using surface passivation, in which the catalytic activity increased more than 14 times for the reduction of nitrobenzene compared with non‐passivated SBA‐15. In addition, this catalyst can selectively catalyze hydrophobic molecules under our experimental conditions, owing to its high (almost superhydrophobic) hydrophobic properties.  相似文献   
110.
1-Alkynylphosphonates 3 are prepared in a one-pot procedure from diethyl phosphorochloridates 2 and alkynyllithiums 1, which are readily generated by the reaction of 1-alkynes with n-BuLi.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号